Near infrared absorbing fine particle dispersion liquid and method for producing the same, anti-counterfeit ink composition using near infrared absorbing fine particle dispersion liquid, and anti-counterfeit printed matter using near infrared absorbing fine particles

ABSTRACT

Provided are a near infrared absorbing fine particle dispersion liquid having an absorption ability in a near infrared region, a clear contrast, and applicable to offset printing, and a method for producing the same, an anti-counterfeit ink composition using the near infrared absorbing fine particle dispersion liquid and an anti-counterfeit printed matter using near infrared absorbing fine particles. Also provided are a near infrared absorbing fine particle dispersion liquid containing a solvent of one or more kinds selected from vegetable oils or vegetable oil-derived compounds; near infrared absorbing fine particles in an amount of 2 mass % or more and 25 mass % or less, selected from one or more kinds of hexaboride fine particles expressed by a general formula XBa (wherein element X is at least one or more kinds selected from a group consisting of La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca, satisfying 4.0≤a≤6.2); and a dispersant soluble in the solvent and having a fatty acid in its structure, wherein viscosity is 180 mPa/S or less, and an anti-counterfeit ink composition containing the near infrared absorbing fine particle dispersion liquid. Also provided is an anti-counterfeit printed matter excellent in anti-counterfeit effect due to the printed matter containing the near infrared absorbing fine particles.

This application is Continuation of application Ser. No. 15/546,923,filed Jul. 27, 2017, which is a national stage of PCT/JP2016/052399,filed Jan. 27, 2016, which claims priority to Japanese PatentApplication No. 2015-012896, filed Jan. 27, 2015. The contents of theprior applications are incorporated by reference herein in theirentireties.

TECHNICAL FIELD

The present invention relates to a near infrared absorbing fine particledispersion liquid having absorption ability in a near infrared regionand applicable to offset printing and a method for producing the same,an anti-counterfeit ink composition using the near infrared absorbingfine particle dispersion liquid, and an anti-counterfeit printed matterusing the near infrared absorbing fine particles. In the presentinvention, the “near infrared absorbing fine particles” and the “nearinfrared absorbing material fine particles” in the prior applicationbased on the priority right are the same fine particles.

DESCRIPTION OF RELATED ART

There are various kinds of printing technologies depending on thepurpose and the like. Among them, offset printing enables high-precisionprinting and has characteristics that it is suitable for mass printing.In the offset printing, the following properties are required: a pigmentdispersion liquid to be used based on its printing principle islipophilic and does not dissolve a rubber blanket to which thedispersion liquid is transferred during the offset printing.

Meanwhile, in recent years, for example, for the purpose of preventionof counterfeiting and the like, the following matter is studied. Data isprinted on various tickets, certificates and the like using a pigmentusing an infrared absorbing material, and the data is read by aninfrared judging device or the like to thereby manage variousinformation.

In such an application, a large amount of data is printed on a largeamount of paper medium, and therefore use of the offset printing as aprinting method has been studied.

Also, when an infrared absorbing material is transparent in a visiblelight region, it can not be distinguished visually that the infraredabsorbing material is printed as a pigment. This is preferable from aviewpoint of prevention of counterfeiting and the like, and is alsopreferable from a viewpoint of visibility and a beautiful appearancebecause it does not visually obstruct an original print display.

As an example using the infrared absorbing material, patent document 1proposes an anti-counterfeit printed matter using a phthalocyaninecompound.

Further, patent document 2 proposes an anti-counterfeit printed matterusing tin-doped indium oxide.

Meanwhile, inventors of the present invention disclose a coatingsolution for a selectively permeable membrane in which hexaboride fineparticles are dispersed in an organic solvent, using the hexaboride fineparticles expressed by a general formula XB_(a) (wherein element X is atleast one or more kinds selected from a group consisting of La, Ce, Pr,Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca) as a materialhaving high visible light transmittance and near infrared absorbingfunction, in patent document 3 and patent document 4. Further theinventors of the present invention disclose an anti-counterfeit ink inwhich an anti-counterfeit ink composition containing the hexaboride fineparticles is dispersed in a solvent as a near infrared absorbingmaterial, in patent document 5.

[Patent Document 1] Japanese Patent Application Laid-Open PublicationNo. 1992-320466 [Patent Document 2] Japanese Patent ApplicationLaid-Open Publication No. 2000-309736 [Patent Document 3] JapanesePatent Application Laid-Open Publication No. 1999-181336 [PatentDocument 4] Japanese Patent Application Laid-Open Publication No.2000-96034 [Patent Document 5] Japanese Patent Application Laid-OpenPublication No. 2004-168842 SUMMARY OF THE INVENTION Problem to beSolved by the Invention

According to studies by the inventors of the present invention, anorganic pigment such as a phthalocyanine compound used in patentdocument 1 has a problem as follows. An infrared absorption property ischanged due to an influence of temperature, ultraviolet rays or thelike, and durability is inferior.

Further, the infrared absorbing material using tin-doped indium oxide,which is used in patent document 2, has insufficient contrast of avisible light that exists in a wavelength region for transmitting andreflecting the light, and an infrared light that exists in a wavelengthregion for absorbing the light. Therefore, when the near infraredabsorbing fine particle dispersion liquid using the tin-doped indiumoxide is applied to the offset printing, there is a problem that readingaccuracy of a printing section and the like are deteriorated.

In contrast, in the selectively permeable membrane coating solution andanti-counterfeit ink described in patent documents 3 to 5, the nearinfrared absorbing fine particles are dispersed in an organic solventsuch as ethanol or toluene. Therefore, in these coating solutions andinks, there is a possibility that the organic solvent dissolves therubber blanket, and therefore they cannot be used as the ink for offsetprinting.

Therefore, the inventors of the present invention attempt to obtain adispersion liquid by using vegetable oils or vegetable oil-derivedcompounds as a solvent for offset printing, and adding to the solventhexaboride fine particles expressed by a general formula XB_(a) (whereinelement X is at least one or more kinds selected from a group consistingof La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, andCa, satisfying 4.0≤a≤6.2). However, it is found that there is a problemthat viscosity of the obtained dispersion liquid is increased and it isdifficult to pulverize the hexaboride fine particles or disperse thehexaboride fine particles in the solvent.

Under such a circumstance, the present invention is provided, and anobject of the present invention is to provide a near infrared absorbingfine particle dispersion liquid having an absorption ability in a nearinfrared region, a clear contrast, and applicable to offset printing,and a method for producing the same.

Further, an object of the present invention is to provide ananti-counterfeit printed matter enabling the offset printing, which isimpossible to be duplicated in copying and the like, and whoseauthenticity can be mechanically and reliably judged not depending on avisual judgment, having few restrictions in design, and excellent inanti-counterfeit effect, by using the anti-counterfeit ink compositioncontaining the near infrared absorbing fine particle dispersion liquid.

Means for Solving the Problem

In order to solve the abovementioned problem, an intensive research isperformed by the inventors of the present invention, and as a result, itis found that instead of adding near infrared absorbing fine particlesto a solvent of one or more kinds selected from vegetable oils orvegetable oil-derived compounds and pulverizing and dispersing them, thenear infrared absorbing fine particles are added to a solvent of one ormore kinds selected from alcohols, ethers, esters, ketones, aromatichydrocarbons and glycol ethers and having a boiling point of 180° C. orless (referred to as “a first solvent” hereafter in some cases in thepresent invention), pulverized and dispersed therein, and further thefirst solvent is replaced with a solvent of one or more kinds selectedfrom vegetable oils or vegetable oil-derived compounds (referred to as“a second solvent” hereafter in some cases in the present invention), tothereby obtain a near infrared absorbing fine particle dispersionliquid.

Further, the inventors of the present invention achieve ananti-counterfeit ink composition for offset printing containing a nearinfrared absorbing fine particle dispersion liquid as described above orcontaining a pigment commonly used in ordinary offset printing inktogether with the abovementioned near infrared absorbing fine particledispersion liquid, and an anti-counterfeit printed matter printed usingthe anti-counterfeit ink composition for offset printing. Thus, thepresent invention is completed.

Namely, in order to solve the abovementioned problem, a first inventionis a near infrared absorbing fine particle dispersion liquid,containing:

a solvent of one or more kinds selected from vegetable oils or vegetableoil-derived compounds;

near infrared absorbing fine particles selected from one or more kindsselected from hexaboride fine particles expressed by a general formulaXB_(a) (wherein element X is at least one or more kinds selected from agroup consisting of La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm,Yb, Lu, Sr, and Ca, satisfying 4.0≤a≤6.2); and a solvent of one or morekinds selected from alcohols, ethers, esters, ketones, aromatichydrocarbons and glycol ethers and having a boiling point of 180° C. orless, wherein content of the solvent of one or more kinds selected fromalcohols, ethers, esters, ketones, aromatic hydrocarbons and glycolethers is 5 mass % or less.

A second invention is the near infrared absorbing fine particledispersion liquid of the first invention, wherein the near infraredabsorbing fine particle dispersion liquid further contains a dispersantwhich is soluble in the solvent of one or more kinds selected from thevegetable oils or vegetable oil-derived compounds and has a fatty acidin its structure, and

a concentration of hexaboride in the near infrared absorbing fineparticle dispersion liquid is 25 mass % or more and 75 mass % or less.

A third invention is the near infrared absorbing fine particledispersion liquid of the second invention, wherein an anchor portion ofthe dispersant has one or more kinds selected from a secondary aminogroup, a tertiary amino group, and a quaternary ammonium group.

A fourth invention is the near infrared absorbing fine particledispersion liquid of the second or third invention, wherein thedispersant has an acid value of 1 mg KOH/g or more.

A fifth invention is the near infrared absorbing fine particledispersion liquid of any one of the first to fourth inventions, whereina dispersed particle size of each near infrared absorbing fine particleis 1 nm or more and 200 nm or less.

A sixth invention is the near infrared absorbing fine particledispersion liquid of any one of the first to fifth inventions, wherein alattice constant of each near infrared absorbing fine particle is 0.4100nm or more and 0.4160 nm or less.

A seventh invention is the near infrared absorbing fine particledispersion liquid of any one of the first to sixth inventions, wherein asurface of the near infrared absorbing fine particle is coated with acompound of one or more kinds selected from Si, Ti, Al, and Zr.

An eighth invention is the near infrared absorbing fine particledispersion liquid of any one of the first to seventh inventions, thevegetable oil is one or more kinds of vegetable oils selected fromdrying oil and semidrying oil.

A ninth invention is the near infrared absorbing fine particledispersion liquid of any one of the first to eighth inventions, whereinthe near infrared absorbing fine particle dispersion liquid furthercontains a binder.

A tenth invention is a method for producing the near infrared absorbingfine particle dispersion liquid, including:

mixing and dispersing near infrared absorbing fine particles of one ormore kinds selected from hexaboride fine particles expressed by ageneral formula XB₆ (wherein element X is at least one or more kindsselected from a group consisting of La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y,Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca, satisfying 4.0≤a≤6.2) in a solventof one or more kinds selected from alcohols, ethers, esters, ketones,aromatic hydrocarbons and glycol ethers and having a boiling point of180° C. or less, to thereby obtain a first dispersion liquid;

adding and mixing a solvent of one or more kinds selected from vegetableoils and vegetable oil-derived compounds in the first dispersion liquid,to thereby obtain a second dispersion liquid; and

-   -   removing from the second dispersion liquid the solvent of one or        more kinds selected from alcohols, ethers, esters, ketones,        aromatic hydrocarbons and glycol ethers and having a boiling        point of 180° C. or less, so that the content of the solvent        becomes 5 mass % or less.

An eleventh invention is the method for producing the near infraredabsorbing fine particle dispersion liquid of the tenth invention,wherein a concentration of the near infrared absorbing fine particles inthe first dispersion liquid is 5 mass % or more and 50 mass % or less.

A twelfth invention is a method for producing a near infrared absorbingfine particle dispersion liquid, including:

mixing a solvent of one or more kinds selected from alcohols, ethers,esters, ketones, aromatic hydrocarbons and glycol ethers and having aboiling point of 180° C. or less, and a solvent of one or more kindsselected from vegetable oils or vegetable oil-derived compounds, tothereby obtain a mixed solvent; and

mixing and dispersing in the mixed solvent the near infrared absorbingfine particles of one or more kinds selected form hexaboride fineparticles expressed by a general formula XB_(a) (wherein element X is atleast one or more kinds selected from a group consisting of La, Ce, Pr,Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, and Ca, satisfying4.0≤a≤6.2), to thereby obtain a third dispersion liquid; and

removing from the third dispersion liquid the solvent of one or morekinds selected from alcohols, ethers, esters, ketones, aromatichydrocarbons and glycol ethers and having a boiling point of 180° C. orless, so that the content of the solvent becomes 5 mass % or less.

A thirteenth invention is the method for producing the near infraredabsorbing fine particle dispersion liquid of the twelfth invention,wherein a concentration of the near infrared absorbing fine particles inthe third dispersion liquid is 5 mass % or more and 50 mass % or less.

A fourteenth invention is the method for producing the near infraredabsorbing fine particles of any one of the tenth to thirteenthinventions, wherein a dispersant which is soluble in the solvent and hasa fatty acid in its structure is added to the solvent of at least one ormore kinds selected from the vegetable oils or vegetable oil-derivedcompounds.

A fifteenth invention is an anti-counterfeit ink composition, containingthe near infrared absorbing fine particles of any one of the first toninth inventions.

A sixteenth invention is the anti-counterfeit ink composition of thefifteenth invention, further containing a pigment.

A seventeenth invention is an anti-counterfeit ink composition, whereinthe pigment of the sixteenth invention is an inorganic pigment, and isone or more kinds selected from carbon black, white pigment, an extenderpigment, a red pigment, a yellow pigment, a green pigment, a bluepigment, a purple pigment, a fluorescent pigment, a temperatureindicating pigment, a pearl pigment, and a metal powder pigment.

An eighteenth invention is an anti-counterfeit ink composition, whereinthe pigment of the sixteenth invention is an organic pigment and is oneor more kinds selected from an azo lake pigment, an insoluble azopigment, a condensed azo pigment, a phthalocyanine pigment, and acondensed polycyclic pigment.

A nineteenth invention is the anti-counterfeit ink composition of anyone of the fifteenth to eighteenth inventions, containing one or morekinds selected from a plasticizer, an antioxidant, a thickener, and awax.

A twentieth invention is an anti-counterfeit printed matter, having aprinted pattern on one side or both sides of a base material, andcontaining near infrared absorbing fine particles of one or more kindsselected from hexaboride fine particles expressed by a general formulaXB_(a) (wherein element X is at least one or more kinds selected from agroup consisting of La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm,Yb, Lu, Sr, and Ca, satisfying 4.0≤a≤6.2), in the printed pattern.

A twenty-first invention is the anti-counterfeit printed matter of thetwentieth invention, wherein the printed pattern further contains apigment.

A twenty-second invention is the anti-counterfeit printed matter of thetwenty-first invention, wherein a pigment is an inorganic pigment and isone or more kinds selected from carbon black, white pigment, an extenderpigment, a red pigment, a yellow pigment, a green pigment, a bluepigment, a purple pigment, a fluorescent pigment, a temperatureindicating pigment, a pearl pigment, and a metal powder pigment.

A twenty-third invention is the anti-counterfeit printed matter of thetwenty-first invention, wherein a pigment is an organic pigment, and isone or more kinds selected from an azo lake pigment, an insoluble azopigment, a condensed azo pigment, a phthalocyanine pigment, and acondensed polycyclic pigment.

A twenty-fourth invention is the anti-counterfeit printed matter of anyone of the twentieth to twenty-third inventions, wherein a valueobtained by dividing an average value of a diffuse reflectance of theanti-counterfeit printed matter in a wavelength range of 800 nm to 1300nm, by an average value of a diffuse reflectance of a blank notcontaining near infrared absorbing fine particles in a wavelength rangeof 800 nm to 1300 nm, is 0.84 or less.

Advantage of the Invention

By using the near infrared absorbing fine particle dispersion liquid ofthe present invention, it is possible to easily perform offset printinghaving an absorption ability in a near infrared region and a clearcontrast. Further, by using the near infrared absorbing fine particledispersion liquid of the present invention, it is possible to provide ananti-counterfeit ink composition enabling offset printing, and ananti-counterfeit printed matter which is impossible to be duplicated incopying and the like, and whose authenticity can be judged mechanicallyand reliably not depending on a visual judgment, having few restrictionsin design, and excellent in anti-counterfeit effect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a light transmission profile of a dried film of a dispersionliquid B according to the present invention.

FIG. 2 is a light transmission profile of a dried film of a dispersionliquid C according to the present invention.

FIG. 3 is a light transmission profile of a dried film of a dispersionliquid D according to the present invention.

FIG. 4 is a light transmission profile of a dried film of a dispersionliquid F according to the present invention.

FIG. 5 is a schematic view of an aspect of a polymer dispersant used inthe present invention.

FIG. 6 is a schematic view of an aspect of another different polymerdispersant used in the present invention.

FIG. 7 is a schematic view of an aspect of further another differentpolymer dispersant used in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Embodiment of the present invention will be described in detail in anorder of near infrared absorbing fine particles, a solvent, adispersant, a method for dispersing near infrared absorbing fineparticles in the solvent, a near infrared absorbing fine particledispersion liquid, an anti-counterfeit ink composition for offsetprinting, a printing method, and an authenticity judging method.

1. Near Infrared Absorbing Fine Particles

The near infrared absorbing fine particles used in the present inventionare hexaboride fine particles expressed by a general formula XB_(a)(4.0≤a≤6.2). Wherein, element X is at least one or more kinds selectedfrom La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr andCa.

Specifically, it is preferable to use one or more kinds selected fromlanthanum hexaboride LaB₆, cerium hexaboride CeB₆, praseodymiumhexaboride PrB₆, neodymium hexaboride NdB₆, hexadentate gadolinium GdB₆,terbium hexaboride TbB₆, dysprosium hexaboride DyB₆, holmium hexaborideHoB₆, yttrium hexaboride YB₆, samarium hexaboride SmB₆, europiumhexaboride EuB₆, erbium hexaboride ErB₆, thulium hexaboride TmB₆,ytterbium hexaboride YbB₆, lutetium hexaboride LuB₆, lanthanumhexaboride cerium (La, Ce)B₆, strontium hexaboride SrB₆, and calciumhexaboride CaB₆.

It is preferable that a surface of each hexaboride fine particle is notoxidized. However, its surface is usually slightly oxidized in manycases, and it is inevitable to some extent that oxidation occurs on thesurface in a fine particle dispersing step. Even in that case, there isno change in effectiveness of developing a heat ray shielding effect,and accordingly it is possible to use even the hexaboride fine particlewhose surface is oxidized.

Further, the abovementioned hexaboride fine particles have a higher heatray shielding effect as crystallinity becomes higher. Even if thehexaboride fine particles have low crystallinity and produce broaddiffraction peaks by X-ray diffraction, a desired heat ray shieldingeffect can be exhibited when a basic bond inside the fine particle iscomposed of a bond between each metal and boron and a lattice constantis 0.4100 nm or more and 0.4160 nm or less, and therefore the hexaboridefine particles can be preferably used in the present invention. Thelattice constant can be obtained by conducting a Rietveld analysis basedon data of an XRD pattern, for example.

It is also preferable that the surface of the hexaboride fine particleis coated with a silane coupling agent. Since the surface of hexaboridefine particle is coated with a silane coupling agent, excellentdispersibility of hexaboride fine particles can be obtained. This isbecause in the near infrared absorbing fine particle dispersion liquidof the present invention, excellent near infrared absorbing function andtransparency in the visible light region can be obtained as a result ofthe excellent dispersibility.

In a film in which the hexaboride fine particles of the presentinvention are sufficiently finely and uniformly dispersed, it isobserved that a light transmittance has a maximum value betweenwavelengths 400 nm and 700 nm and has a minimum value betweenwavelengths 700 nm and 1800 nm, and further a difference between themaximum value and the minimum value in the transmittance of the light is15 points or more.

A wavelength of a visible light is 380 nm to 780 nm and a humanvisibility takes a bell-type form with its peak at around 550 nmwavelength. When this is taken into consideration, it is found that sucha heat ray shielding transparent resin molded product effectivelytransmits visible lights and effectively reflects and absorbs other heatrays.

The hexaboride fine particles of the present invention largely absorb alight in a near ultraviolet region near a wavelength range of 350 to 400nm and in the near infrared region near a wavelength range of 650 to1300 nm, and particularly a light near a wavelength of 1000 nm.Therefore, a transmission color tone is from colorless to greenish inmany cases.

Further, the dispersed particle size of each hexaboride fine particle ofthe present invention can be selected according to the intended use. Forexample, in order for the hexaboride fine particles of the presentinvention to exhibit absorption in the near infrared region, it ispreferable to sufficiently decrease a dispersed particle size of eachhexaboride fine particle. This is because absorption by hexaboride iscaused by localized surface plasmon resonance which is a phenomenonpeculiar to nanoparticles. Here, the dispersed particle size means anaggregated particle size of boride fine particles in a solvent, and itcan be measured using various commercially available particle sizedistribution meters. For example, sampling is performed from adispersion liquid in which boride fine particles are dispersed in asolvent, with aggregates of boride fine particles also present therein,so that the dispersed particle size can be measured using ELS-800manufactured by Otsuka Electronics Co., Ltd. based on a principle ofdynamic light scattering method. For example, when the dispersedparticle size is 1500 nm or less, the hexaboride fine particles haveabsorption in the near infrared region. Then, when the dispersedparticle size of the hexaboride fine particles is about 800 nm or less,the absorption in the near infrared region becomes strong, and when itis 200 nm or less, stronger absorption is exhibited, and when it is 100nm or less, further stronger absorption is exhibited.

On the other hand, in the hexaboride fine particles of the presentinvention, transparency/non-scattering property in the visible lightregion can be obtained by suppressing a light scattering caused by thefine particles. As the light scattering, there are geometric opticalscattering, Mie scattering, and Rayleigh scattering, depending on theratio of the particle size to a light wavelength.

In a case of the visible light, geometric optical scattering can bealmost ignored as long as the dispersed particle size of each hexaboridefine particle is 1000 nm or less. Then, when the dispersed particle sizeis 200 nm or less, Mie scattering is weakened, and when it is 100 nm orless, further weakening is achieved. Rayleigh scattering is a mainscattering factor in a region where the dispersed particle size of thefine particle is further smaller. Then, Rayleigh scattering intensity isdecreased in inverse proportion to sixth power of the dispersed particlesize, and therefore the scattering light can be reduced by furtherdecreasing the dispersed particle size of the fine particles, and thisis preferable.

The hexaboride fine particle dispersion liquid of the present inventionis used as a raw material for anti-counterfeit ink for offset printing,and when this is further taken into consideration in view of the abovematter, the dispersed particle size of the hexaboride fine particle ofthe present invention is preferably 200 nm or less. This is because whenthe dispersed particle size is 200 nm or less, near infrared absorptionof hexaboride by localized surface plasmon resonance is sufficientlyexhibited and light scattering of the visible light is sufficientlyreduced, and therefore the contrast of [reflection/absorption] or[transmission/absorption] of the light reflected by the surface of theprinted matter or the light transmitted through the printed matter, isimproved. On the other hand, when the dispersed particle size is 1 nm ormore, industrial production is easy.

It is preferable that the surface of the hexaboride fine particle of thepresent invention is coated with an oxide containing at least one ormore kinds of Si, Ti, Zr and Al, from a viewpoint of improving a weatherresistance of the hexaboride fine particles.

2. Solvent <First Solvent>

A first solvent used in the present invention is a solvent suitable forpulverizing the hexaboride of the present invention into fine particlesand dispersing it in the solvent.

Specifically, it is preferable to use each kind of solvent such asalcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutylalcohol and diacetone alcohol, ethers such as methyl ether, ethyl etherand propyl ether, esters, ketones such as acetone, methyl ethyl ketone,diethyl ketone, cyclohexanone, ethyl isobutyl ketone, methyl isobutylketone, aromatic hydrocarbons such as toluene, xylene and benzene, andglycol ethers such as propylene glycol monomethyl ether acetate andpropylene glycol monoethyl ether, and having affinity with a secondsolvent described later.

In addition to this point of view, solvents such as alcohols and glycolethers are low in health hazard to a human body, and are preferablesolvents from a viewpoint of safety in the process and operability.Further, methyl isobutyl ketone and toluene are preferable solventsexcellent in workability and are preferable solvents from a viewpoint ofimproving productivity.

Offset printing is a printing method that utilizes a property that waterand oil repel each other, and a plate is made up of a lipophilic layerto which printing ink is applied and a new water layer to which water isapplied and printing ink is not applied. Therefore, offset printing inkand water are required to be hardly soluble each other. Among the firstsolvents, alcohols and glycol ethers are highly polar and easily solublein water, and therefore in the offset printing ink, a predeterminedamount or less of alcohols and glycol ethers are required to becontained. Specifically, the content of alcohols and glycol ethers ispreferably 1.0 mass % or less.

Further, although solvents other than alcohols and glycol ethers arepoor in polarity and hardly soluble in water, they may possibly dissolvea rubber blanket to which a dispersion liquid of fine particles istransferred during offset printing, and therefore in the offset printingink, a predetermined amount or less of them are required to becontained. Specifically, the content of them are preferably 1.0 mass %or less.

Accordingly, after pulverizing the hexaboride of the present inventioninto fine particles and dispersing them in a solvent, it is preferablethat the content of the first solvent is sufficiently reduced.

Specifically, it is conceivable that a solvent having a low boilingpoint is used as the first solvent, a difference in boiling point isprovided between the first solvent and the second solvent, and thecontent of the first solvent is reduced by heating distillation.

When a solvent substitution by heating distillation is performed, it ispreferable to use a solvent having a boiling point of 180° C. or less,as the first solvent.

<Second Solvent>

The second solvent used in the present invention is required to bewater-insoluble and not dissolve the rubber blanket used in the offsetprinting. Specifically, the solvent of one or more kinds selected fromvegetable oils and vegetable oil-derived compounds can be used.

Drying oils such as linseed oil, sunflower oil and tung oil, semidryingoils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, ricebran oil, non-drying oils such as olive oil, coconut oil, palm oil,dehydrated castor oil and the like, can be used as vegetable oils. Fattyacid monoesters or ethers obtained by directly esterifying fatty acid ofvegetable oil and monoalcohol, can be used as the vegetable oil-derivedcompounds.

The abovementioned vegetable oils and vegetable oil-derived compoundshave double bonds in fatty acid which is a constituent component of oiland fat contained therein. Such a double bond reacts with oxygen in theair, whereby a polymerization reaction proceeds between the molecules ofthe fat/oil having the double bond, and between fat/oil having thedouble bond and a pigment component having the double bond. Thepolymerization reaction proceeds by polymerization of the molecules ofthe oil and fat and polymerization of oil and fat with pigmentcomponents or the like for offset printing, to thereby solidify acoating film after offset printing.

The solidification of the coating film after offset printing becomesfaster as the number of double bonds in the fatty acid as a constituentcomponent of the vegetable oils and the vegetable oil-derived compoundsis larger, and the number of the double bonds in the fatty acid isevaluated by iodine value. Namely, the solidification of the coatingfilm becomes faster as the iodine value of the vegetable oil-derivedcompounds or vegetable oils is higher. Here, the drying oil has aniodine value of 130 or more, the semidrying oil has 130 to 100, and thenon-drying oil has 100 or less. Then, one or more kinds selected fromsemi-drying oil, drying oil such as linseed oil, sunflower oil, tung oiland the like having an iodine value of 130 or more, are preferable, asthe vegetable oils and the vegetable oil-derived compounds used for theoffset printing.

3. Dispersant

From a viewpoint of improving workability and operability, it is alsopreferable that by adding a dispersant to the first solvent and thesecond solvent in which the hexaboride fine particles of the presentinvention are dispersed, or to the first and second mixed solvents, theviscosity of the solvent is lowered. From a viewpoint of lowering theviscosity of the solvent, it is preferable that the added dispersant ofthe present invention has a fatty acid in its structure.

Specifically, the dispersant of the present invention is required to besoluble in the abovementioned first and second solvents of the presentinvention.

Further, when the acid value of the dispersant of the present inventionis 1 mg KOH/g or more, this is preferable because the ability ofdispersing the abovementioned near infrared absorbing fine particles inthe solvent of the present invention is high. From this viewpoint, thestructure of the dispersant of the present invention is not particularlylimited, but it is preferable to use a polymer dispersant having a basicanchor portion. The anchor portion is a portion (group) in the moleculeof the polymer dispersant and is a part (group) that is adsorbed on thesurface of the near infrared absorbing fine particle.

In the present invention, when the polymer dispersant havingparticularly the basic anchor portion is used, storage stability of theink is improved, which is preferable. As a basic part (group) serving asthe anchor portion, there are parts (groups) such as a secondary aminogroup, a tertiary amino group, and a quaternary ammonium group.

An aspect of the polymer dispersant used in the present invention isshown in FIG. 5. In the general formula [X−A1−Y−A2−Z], A1 and A2 areportions (anchor portions) which are adsorbed on solid fine particles.In the anchor portion, its structure is not particularly limited as longas it has at least one point (adsorption point) to be adsorbed on eachsolid fine particle, and has a chain, cyclic, or fused polycyclic shape,or a combination thereof for example. Further, A1 and A2 may be the sameor different. On the other hand, X, Y and Z are polymer chain portionswhich are solvated, and solved and spread out from the surface of thesolid fine particle into a liquid, and hereinafter, X and Z are referredto as tail portions and Y is referred to as a loop portion. In the tailportions and the loop portion, a homopolymer composed of a singlemonomer and a copolymer composed of plural monomers are used.

Further, as the polymer dispersant used in the present invention, asubstance having no loop portion (Y) in the general formula[X−A1−Y−A2−Z], can be used, which is synonymous with the general formula[X−A1−A2−Z].

Still further, as an aspect of the polymer dispersant used in thepresent invention, there is also a structure in which Y shown in FIG. 6does not exist and two tail portions are bonded to one anchor portion.In this case, the general formula is [X−A3−Z].

In addition, as an aspect of the polymer dispersant used in the presentinvention, there is also a structure in which Z shown in FIG. 7 does notexist and one tail portion is bonded to one anchor portion. In thiscase, the general formula is [X−A4].

“A” constituting the polymer dispersant used in the present invention(in the present invention, A1, A2, A3, and A4 described above may becollectively referred to as “A” in some cases), has for example at leastone adsorption point (functional group) having an adsorption interactionwith the surface of the solid particle by hydrogen bonding or anacid-base interaction or the like. Further, although A1 and A2 may bethe same or different, A1 and A2 preferably have the same functionalgroup as the functional group having the adsorption interaction at theadsorption point, in consideration of absorptivity to the solid fineparticles.

Next, X, Y and Z constituting the polymer dispersant used in the presentinvention may be composed of different chemical species, and at leasttwo of them may be composed of the same chemical species. Since the tailportions and the loop portion are solvated portions which are solved andspread out from the surface of the solid fine particle into the liquid,the polymer chain having affinity with the solvent for dispersing theabovementioned solid fine particles is used.

The dispersant of the present invention exhibits a dispersing ability ofensuring fluidity of the dispersion liquid in which the hexaboride fineparticles of the present invention are dispersed in an amount of 25 mass% or more and 75 mass % or less, by adding the dispersant in the solventof one or more kinds selected from vegetable oils or vegetableoil-derived compounds.

In a case of a commercially available dispersant as a specific exampleof a preferable dispersant, DISPERBYK 142; Disperbyk 160, Disperbyk 161,Disperbyk 162, Disperbyk 163, Disperbyk 166, Disperbyk 170, Disperbyk180, Disperbyk 182, Disperbyk 184, Disperbyk 190, Disperbyk 2155 (Allmanufactured by BYK Japan K.K.); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (allmanufactured by BASF); SOLSPERSE 11200, Solsperse 13940, Solsperse16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse24000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse33000, Solsperse 39000, Solsperse 56000, Solsperse 71000 (manufacturedby Lubrizol Japan); SOLPLUS Solplus D 530, Solplus DP 320, Solplus L300, Solplus K 500, Solplus R 700 (all manufactured by Lubrizol Japan);Ajisper PB 711, Ajisper PA 111, Ajisper PB 811, Ajisper PW 911(manufactured by Ajinomoto Co., Ltd.); Florel DOPA-15B, Floren DOPA-22,Floren DOPA-17, Floren TG-730W, Floren G-700, Floren TG-720W (allmanufactured by Kyoeisha Chemical Industry Co., Ltd.), etc., can bementioned.

An addition amount of the dispersant of the present invention ispreferably 30 parts by weight or more and 200 parts by weight or lessbased on 100 parts by weight of hexaboride fine particles.

When a commercially available dispersant is used, it is preferable thatthe dispersant does not contain a solvent that may possibly dissolve therubber blanket for offset printing. Accordingly, a nonvolatile content(after heating at 180° C. for 20 minutes) of the dispersant ispreferably high, for example, preferably 95% or more.

4. Method for Dispersing the Near Infrared Absorbing Fine Particles inthe Solvent

As described above, since the viscosity of the second solvent is high,it is difficult to disperse the hexaboride fine particles in the secondsolvent. Particularly, it is difficult for solvents such as tung oil tohave a viscosity (24° C.) of 180 mPa/S or more.

Therefore, as a method for dispersing the near infrared absorbing fineparticles in the solvent, a method for producing the first and secondnear infrared absorbing fine particle dispersion liquids can beconsidered. The method for producing the first and second near infraredabsorbing fine particle dispersion liquids will be described hereafter.

(1) Method for Producing the First Near Infrared Absorbing Fine ParticleDispersion Liquid

There is provided the method for producing the near infrared absorbingfine particle dispersion liquid, including:

mixing the hexaboride fine particles into the first solvent andperforming dispersion treatment using a wet medium mill or the like toobtain a first dispersion liquid;

adding a solvent of one or more kinds selected from vegetable oils orvegetable oil-derived compounds to the first dispersion liquid andmixing them to obtain a second dispersion liquid; and

removing the first solvent from the second dispersion liquid until acontent of the first solvent becomes 5 mass % or less.

Explanation will be given hereafter in detail.

The dispersion method for obtaining the first dispersion liquid bydispersing the hexaboride fine particles of the present invention in thefirst solvent of one kind or more, can be arbitrarily selected as longas the fine particles are uniformly dispersed in the solvent.Specifically, it is preferable to use a wet medium mill such as a beadmill or a ball mill. The first solvent is a solvent having a boilingpoint of 180° C. or less, preferably a boiling point of 150° C. or less.

When the concentration of the hexaboride fine particles in the firstdispersion liquid is 5 mass % or more, productivity in producing theanti-counterfeit ink composition for offset printing is excellent. Incontrast, when the concentration of the hexaboride fine particles is 50mass % or less, the viscosity of the first dispersion liquid is notexcessively high, thus facilitating the pulverization and dispersion ofthe hexaboride fine particles.

From this viewpoint, the concentration of the hexaboride fine particlesin the first dispersion liquid is preferably from 5 to 50 mass %, morepreferably from 10 to 40 mass %, still more preferably from 20 to 30mass %.

The second solvent of one or more kinds selected from the vegetable oilsor the vegetable oil-derived compounds, is added and mixed into thefirst dispersion liquid in which the hexaboride fine particles aredispersed, to thereby obtain the second dispersion liquid. At this time,it is preferable to select the solvents which are soluble each other, asthe first solvent and the second solvent.

When the mixing of the first dispersion liquid and the second solvent isperformed in such a manner that the second solvent is 2.5 parts byweight or more based on 100 parts by weight of the hexaboride fineparticles contained in the first dispersion liquid, the finally obtainedfluidity of the near infrared absorbing fine particle dispersion liquidof the present invention is kept, recovery is facilitated, andproductivity is maintained.

In contrast, when the second solvent is 270 parts by weight or lessbased on 100 parts by weight of the hexaboride fine particles containedin the first dispersion liquid, the concentration of hexaboride fineparticles in the finally obtained near infrared absorbing fine particledispersion liquid of the present invention is ensured. Therefore, it ispossible to avoid adding a large amount of the near infrared absorbingfine particle dispersion liquid of the present invention, and it ispossible to ensure the viscosity of the ink. As a result, viscosityadjustment is not required, the process is simplified and an increase inproduction cost can be avoided, which is preferable.

From the abovementioned viewpoint, the mixing of the first dispersionliquid and the second solvent is preferably performed in such a mannerthat the second solvent is 2.5 to 270 parts by weight, more preferably70 to 270 parts by weight, and still more preferably 92 to 204 parts byweight based on 100 parts by weight of the hexaboride fine particlescontained in the first dispersion liquid.

When increase of the viscosity of the first and second dispersionliquids is desired to be further suppressed in dispersing the hexaboridefine particles in the solvent of one or more kinds to obtain the firsthexaboride fine particle dispersion liquid, and adding and mixing thesecond solvent of one or more kinds thereto to obtain the seconddispersion liquid, it is also preferable to add the abovementioneddispersant. As a method for adding the dispersant, it is possible toemploy methods such as (i) adding a dispersant to the first solvent,(ii) adding a dispersant to the second solvent in advance to prepare adispersant solution and adding the dispersant solution to the firstdispersion liquid (iii) adding a dispersant to the first dispersionliquid in parallel with the addition of the second solvent. In the caseof using the method of (i) adding a dispersant to the first solvent, adispersant soluble in the first solvent is selected.

Next, the first solvent is removed from the second dispersion liquid andthe content of the first solvent in the second dispersion liquid isadjusted to 5 mass % or less to obtain the near infrared absorbing fineparticle dispersion liquid of the present invention.

For removing the first solvent from the second dispersion liquid, athermal distillation method using a difference in boiling points in thefirst and second solvents can be used. Further, according to adepressurization heating distillation method in which the depressurizingoperation is also added to the heating distillation method, this is apreferable configuration also from the viewpoint of safety, energy cost,and stabilization of quality.

(2) Method for Producing the Second Near Infrared Absorbing FineParticle Dispersion Liquid

There is provided a method for producing the near infrared absorbingfine particle dispersion liquid, including:

mixing the first solvent and the second solvent to obtain a mixedsolvent;

mixing the hexaboride fine particles in the mixed solvent and performingdispersion treatment by a wet medium mill to obtain a third dispersionliquid; and

removing the first solvent from the third dispersion liquid until thecontent of the first solvent becomes 5 mass % or less.

Explanation will be given hereafter in detail.

The abovementioned first solvent of one or more kinds and the secondsolvent of one or more kinds are previously mixed to obtain a mixedsolvent. At this time, it is preferable to select the solvents which aresoluble each other, as the first solvent and the second solvent. Thedispersion method for obtaining the third dispersion liquid bydispersing the hexaboride fine particles of the present invention inthis mixed solvent, can be arbitrarily selected as long as the fineparticles are uniformly dispersed in the solvent. Specifically, it ispreferable to use a wet medium mill such as a bead mill or a ball mill.

When the concentration of the hexaboride fine particles in the thirddispersion liquid is 5 mass % or more, productivity in manufacturing theanti-counterfeit ink composition for offset printing is excellent. Incontrast, when the concentration of the hexaboride fine particles is 50mass % or less, the viscosity of the third dispersion liquid is notexcessively high, thus facilitating the pulverization and dispersion ofthe hexaboride fine particles.

From this viewpoint, the concentration of the hexaboride fine particlesin the third dispersion liquid is preferably from 5 to 50 mass %, morepreferably from 10 to 40 mass %, still more preferably from 20 to 30mass %.

When increase of the viscosity of the mixed solvent in which thehexaboride fine particles are added is desired to be further suppressed,it is also preferable to add the abovementioned dispersant. As a methodfor adding the dispersant, the dispersant may be added to the mixedsolvent before the operation of dispersing the hexaboride fineparticles.

Next, the first solvent is removed from the mixed solvent in which thehexaboride fine particles are dispersed, and the first solvent contentin the mixed solvent in which the hexaboride fine particles aredispersed is set to 5 mass % or less, to obtain the near infraredabsorbing fine particle dispersion liquid of the present invention.

For removing the first solvent from the mixed solvent in which thehexaboride fine particles are dispersed, it is preferable to use a heatdistillation method to which the depressurizing operation is also added,using a difference in boiling point between the first and secondsolvents.

Specifically, in the heat distillation method to which thedepressurizing operation is also added, the second dispersion liquid isdistilled under reduced pressure while stirring, and the first solventis separated from the second dispersion liquid. Vacuum stirring typedryers can be cited as apparatuses used for heat distillation to whichthe depressurizing operation is also added, but there is no particularlimitation as long as the apparatus has the above functions. Thetemperature during the heat distillation is preferably from 35 to 200°C. The temperature is more preferably from 40 to 150° C., andparticularly preferably from 60 to 120° C. When the temperature duringheating distillation is 35° C. or more, a solvent removal rate can beguaranteed. Meanwhile, when the temperature during heating distillationis 200° C. or less, it is possible to avoid a situation such that thedispersant is deteriorated.

When the depressurizing operation is used in combination with theabovementioned heating distillation, the degree of vacuum is −0.05 MPaor less, more preferably −0.06 MPa or less at gauge pressure. When thegauge pressure is −0.05 Mpa or less, the removal speed of the firstsolvent becomes fast and the productivity is good.

By applying the vacuum distillation method, the solvent removalefficiency is improved and the near infrared absorbing fine particledispersion liquid of the present invention is not exposed to a hightemperature for a long time, agglomeration of the dispersed hexaboridefine particles and deterioration of the second solvent do not occur,which is preferable. Further, productivity is also increased, and anevaporated organic solvent can be easily recovered, which is preferablefrom the viewpoint of environmental consideration.

5. Near Infrared Absorbing Fine Particle Dispersion Liquid

By the production method described above, the near infrared absorbingfine particle dispersion liquid of the present invention is obtained.

The higher the concentration of hexaboride fine particles is in the nearinfrared absorbing fine particle dispersion liquid of the presentinvention, the easier it is to prepare the anti-counterfeit ink foroffset printing, which is preferable. Meanwhile, the higher theconcentration of the hexaboride fine particles is, the lower thefluidity of the hexaboride fine particle dispersion liquid becomes.However, in the abovementioned production method, it is sufficient ifthe fluidity is such that the produced hexaboride fine particledispersion liquid can be recovered.

From this viewpoint, in the near infrared absorbing fine particledispersion liquid of the present invention, a preferable concentrationof hexaboride fine particles is 25 mass % or more and 75 mass % or less,more preferably 25 mass % or more and 50 mass % or less, furtherpreferably 30 mass % or more and 45 mass % or less.

Meanwhile, the dispersed particle size of the hexaboride fine particlescan be arbitrarily controlled by the treatment time using theabovementioned wet type medium mill. Namely, by increasing the treatmenttime, the dispersed particle size can be small.

A lower limit value of the viscosity of the near infrared absorbing fineparticle dispersion liquid of the present invention depends on theviscosity of the used vegetable oils or the vegetable oil-derivedcompounds. For example, the viscosity (24° C.) of sunflower oil is 50mPa/S and the viscosity of linseed oil (24° C.) is 40 mPa/S, and theviscosity of tung oil (24° C.) is 210 mPa/S.

A binder may be further added to the near infrared absorbing fineparticle dispersion liquid of the present invention. The binder is notparticularly limited, and for example, synthetic resins such asrosin-modified phenol resin, rosin-modified alkyd resin and petroleumresin-modified phenolic resin, can be mentioned. Therefore, the bindersuitable for the purpose can be selected.

6. Anti-Counterfeit Ink Composition for Offset Printing

The anti-counterfeit ink composition for offset printing can be obtainedby mixing the near infrared absorbing fine particle dispersion liquid, aresin varnish component, a vegetable oil component, a petroleum solventcomponent, and an additive agent of the present invention.

As the resin varnish component, arbitrary resin system such as phenolresin, petroleum resin, rosin modified phenol resin, petroleum resinmodified rosin modified phenol resin, vegetable oil modified rosinmodified phenol resin, modified alkyd resin, rosin modified maleic acidresin, polyester resin, acrylic resin, urethane resin, and epoxy resin,etc., are preferably used, and for example, a resin varnish using rosinmodified phenol resin or petroleum resin is preferably used.

An addition amount of the resin varnish in the lithographic offsetprinting ink composition is 15 to 70 mass %, preferably 40 to 60 mass %.Further, as the vegetable oil component and the petroleum solventcomponent, any one of those generally used for the lithographic offsetink may be used.

Plasticizers, oxidant inhibitors, thickeners, waxes and the like can bementioned as the additive agent.

Further, in the anti-counterfeit ink composition for offset printing ofthe present invention, it is possible to form a colored pattern in thevisible light region by adding a pigment used for a general lithographicoffset ink. By forming the colored pattern, an effect in terms of adesign can be enhanced, and an anti-counterfeit effect can be enhanced.

As the abovementioned pigment, any pigment may be used as long as itdoes not impair printing suitability. Specifically, various organicpigments such as azo lake pigment, insoluble azo pigment, condensed azopigment, phthalocyanine pigment, condensed polycyclic pigment and thelike can be used. In addition to the organic pigment, various inorganicpigment including carbon black, white pigments such as titanium oxideand white lead, extender pigments such as calcium carbonate, redpigments such as red iron oxide, yellow pigments such as yellow lead,green pigments such as chromium oxide, blue pigments such asultramarine, purple pigment such as manganese violet, and fluorescentpigment, temperature-indicating pigment, pearl pigment, metal powderpigment and the like, can be used.

Further, it is also preferable to use carbon black alone.

In the anti-counterfeit ink composition for offset printing of thepresent invention, as described above, it is possible to simultaneouslyuse the near infrared absorbing fine particles and the pigment used fora general lithographic offset ink. By adopting such a configuration, acolor difference from ordinary offset ink not containing the nearinfrared absorbing fine particles, can be small enough so that it cannotbe visually discriminated.

The near infrared absorbing fine particle dispersion liquid, the resinvarnish component, the petroleum solvent component, the additive, and/orthe pigment of the present invention can be kneaded using a kneadingmachine such as a triple roll mill and the like. At that time, wettingvarnishes such as alkyd resin and other additives that are excellent inwetting properties of an infrared absorbing agent may be used in orderto increase the degree of kneading and to improve working efficiency.

7. Printing Method

As a printing method for providing the printed matter of the presentinvention, a conventionally known lithographic offset printing method isused. For example, offset sheet-fed printing, offset rotary printing,waterless offset printing, dry offset printing, and the like can bementioned.

As a base material used in the printed matter of the present invention,for example, white paper, a plastic film printed in white, and the likecan be mentioned. As the plastic film in this case, polypropylene (PP),polyvinyl chloride (PVC), polyethylene terephthalate (PET), syntheticpaper and the like can be mentioned. Depending on the purpose of use ofthe finished product, it is considered that there is a superiority ofpaper and film respectively, although it cannot be said which is goodunconditionally. However, in the example of the present inventiondescribed later, white pure paper is chosen because of inexpensivenessand ease of handling.

As an anti-counterfeit ink set for offset printing of the presentinvention, conventionally known lithographic offset printing ink isused. For example, oxidation polymerization type ink, heat set type ink,osmotic drying type ink and the like can be mentioned.

Further, conventionally known plate making technology is also used for aplate used for printing.

For example, a plate formed by amplitude modulation screening (AMscreening) method, a plate formed by frequency modulation screening (FMscreening) method, and the like can be mentioned.

By printing using the anti-counterfeit ink composition for offsetprinting of the present invention, a printed matter which is lessrestricted in design and also excellent in the anti-counterfeit effectcan be provided.

8. Authenticity Judging Method

The printed matter of the present invention is irradiated with the nearinfrared rays having a wavelength of 800 nm to 1300 nm, and the nearinfrared rays having the abovementioned wavelength diffusely reflectedfrom the printed matter are measured. The printed matter of the presentinvention has less diffuse reflection of near infrared rays having awavelength of 800 nm to 1300 nm as compared with a blank printed matternot containing the near infrared absorbing fine particles. Therefore,based on a difference between a diffuse reflectance of the printedmatter containing the near infrared absorbing fine particles forreflecting the near infrared ray having a wavelength of 800 nm to 1300nm, and a diffuse reflectance of the blank printed matter for reflectingthe near infrared ray having a wavelength of 800 nm to 1300 nm, theauthenticity of the printed matter can be easily judged. For example, bydividing a diffuse reflectance value of the printed matter of thepresent invention in a wavelength range of 800 nm to 1300 nm, by adiffuse reflectance value of the blank printed matter in a wavelengthrange of 800 nm to 1300 nm, it is possible to evaluate a net diffusereflectance of the near infrared absorbing fine particles excludingfactors such as the binder and other factors and the base material. Thesmaller this divided value is, the easier the authenticity is judged,and 0.84 or less is preferable, 0.77 or less is more preferable.

In order to decrease the value obtained by dividing the diffusereflectance value of the printed matter containing the near infraredabsorbing fine particles, by the diffuse reflectance value of the blankprinted matter, it can be considered that the content of the nearinfrared absorbing fine particles may be increased, and theconcentration of the near infrared absorbing fine particles in the inkmay be increased. However, there is a limit in terms of ink stabilityand cost. In addition, it can be considered that a film thickness isthickened by overcoating the ink. However, there is a concern thatinfluences such as an increase in man-hours and unevenness on a printedsurface due to thickening of the film thickness, etc. are caused.

Accordingly, it is preferable that an amount of the near infraredabsorbing fine particles contained in the printed matter is small, thusleading to use of the near infrared absorbing fine particles of thepresent invention. Specifically, the amount of the near infraredabsorbing fine particles contained in the printed matter is preferably0.8 g/cm² or less.

The diffuse reflectance of the present invention is obtained bymeasuring a relative value of the diffuse reflectance in a wavelengthregion of 800 nm to 1300 nm, with respect to the diffuse reflectance ofa white plate formed by solidifying barium sulfate fine powder, which isadjusted to 100% using a spectrophotometer.

EXAMPLES

The present invention will be specifically described hereafter withreference to examples, but the present invention is not limited to theseexamples.

A method for measuring the acid value of the near infrared absorbingfine particle dispersant of this example complies with JIS K 0070, andperformed by a potentiometric titration method. Further, a method formeasuring the viscosity of the near infrared absorbing fine particledispersion liquid of this example was measured using a vibration typeviscometer VM 100 A-L (manufactured by CBC Materials Co., Ltd.).Further, measurement was performed under the condition of using CuKα rayusing a fine particle X-ray diffractometer (D2 PHASER manufactured byBruker AXS Co., Ltd.), to thereby obtain an XRD pattern of 2θ=10° to100°, and Rietveld analysis was performed based on the XRD pattern tothereby obtain a lattice constant of the near infrared absorbing fineparticles of this examples.

Then, optical properties of the printed matter of this example weremeasured using a spectrophotometer U-4100 (manufactured by Hitachi,Ltd.). The diffuse reflectance was measured as follows: aspectrophotometer U-4100 (manufactured by Hitachi, Ltd.) was prepared sothat the diffuse reflectance of a white board on which fine powder ofbarium sulfate has been hardened was adjusted to 100%, and the diffusereflectance was measured as a relative value of every 5 nm in awavelength region of 800 nm to 1300 nm, and an average value of theobtained values was used.

Example 1

20.0 mass % of lanthanum hexaboride fine particles (average particlesize: 1 to 2 μm) as near infrared absorbing fine particles, 10.0 mass %of a dispersant (abbreviated as dispersant “a” hereafter) having a fattyacid in its structure, having an amino group, having an acid value of20.3 mg KOH/g, having a hydroxystearic acid chain, and having anonvolatile content of 100%, and 70.0 mass % of methyl isobutyl ketone(abbreviated as MIBK hereafter) as a solvent, were weighed.

These hexaboride fine particles, dispersant, and solvent were charged ina paint shaker containing 0.3 mmφ ZrO₂ beads, pulverized and dispersedfor 30 hours, to thereby obtain a hexaboride fine particle dispersionliquid (abbreviated as dispersion liquid A hereafter) of example 1.

Further, 36.6 parts by weight of tung oil was mixed and added to 100parts by weight of solution A, and next, using a stirring vacuum dryer(Ishikawa vacuum evacuator manufactured by Ishikawa Factory), heateddistillation was also performed at 80° C. for 1 hour under reducedpressure operation (−0.08 MPa under gauge pressure), and MIBK wasremoved to thereby obtain a hexaboride fine particle dispersion liquid(hereinafter abbreviated as dispersion liquid B). The concentration ofthe lanthanum hexaboride fine particles in the dispersion liquid B was29.6 mass %.

Here, an amount of residual MIBK in the dispersion liquid B was measuredusing a dry moisture meter (MOC-120H: manufactured by ShimadzuCorporation), and it was found to be 1.5 mass %. The dispersed particlesize of the hexaboride fine particles in the dispersion liquid B wasmeasured by a particle size distribution meter manufactured by OtsukaElectronics Co., and it was found to be 84.6 nm. The lattice constantwas 0.41560 nm.

The results are shown in table 1 (also shown in examples 2, 3, 4 andcomparative example 1 hereafter).

A transparent PET film having a thickness of 50 μm was prepared as asubstrate to be printed and the dispersion liquid B was formed on thesurface thereof with a bar coater to a thickness of 8 μm. This film washeated at 70° C. for 3 hours to dry the dispersion liquid B.

The dried film of the dispersion liquid B thus obtained had a visiblelight transmittance of 69.6%. Further, the transmittance at a wavelengthof 550 nm in a visible light region was 71.5%, the transmittance at awavelength of 800 nm was 30.6%, the transmittance at a wavelength of 900nm was 22.3%, the transmittance at a wavelength of 1000 nm was 20.2%,and the transmittance at a wavelength of 1500 nm was 71.0% in a nearinfrared region. The transmission profile of the dried film of thedispersion liquid B is shown in FIG. 1 and the measurement results areshown in table 1 (also shown in examples 2, 3, and 4 hereafter).

Example 2

A hexaboride fine particle dispersion liquid (abbreviated as adispersion liquid C hereafter) of example 2 was obtained in the samemanner as in example 1 except that 10.0 parts by weight of tung oil wasadded to 100 parts by weight of solution A. The concentration oflanthanum hexaboride fine particles in the dispersion liquid C was 29.2mass %.

An amount of residual MIBK in the dispersion liquid C was measured usinga dry moisture meter, and it was found to be 2.6 mass %. The dispersedparticle size of each hexaboride fine particle in the dispersion liquidC was measured using a particle size distribution meter manufactured byOtsuka Electronics Co., and it was found to be 84.3 nm. Further, thelattice constant was 0.41560 nm.

Next, a dried film of example 2 was obtained in the same manner as inexample 1, and optical properties were measured.

The obtained dried film had a visible light transmittance of 68.8%.Further, the transmittance at a wavelength of 550 nm in the visiblelight region was 70.8%, the transmittance at a wavelength of 800 nm was29.5%, the transmittance at a wavelength of 900 nm was 21.4%, thetransmittance at a wavelength of 1000 nm was 19.3%, and thetransmittance at a wavelength of 1500 nm was 69.8% in the near infraredregion. The transmission profile of the dried film of this dispersionliquid C is shown in FIG. 2.

Example 3

A hexaboride fine particle dispersion liquid of example 3 (abbreviatedas a dispersion liquid D hereafter) was obtained in the same manner asin example 1 except that 36.6 parts by weight of linseed oil was addedand mixed to 100 parts by weight of solution A. The concentration oflanthanum hexaboride fine particles in dispersion liquid D was 29.6 mass%.

An amount of residual MIBK in the dispersion liquid D was measured usinga dry moisture meter, and it was found to be 1.5 mass %. The dispersedparticle size of each hexaboride fine particle in the dispersion liquidD was measured using a particle size distribution meter manufactured byOtsuka Electronics Co., and it was found to be 84.5 nm. Further, thelattice constant was 0.41560 nm.

Next, in the same manner as in example 1, a dried film of example 3 wasobtained and the optical properties were measured.

The obtained dried film had a visible light transmittance of 68.4%.Further, the transmittance at a wavelength of 550 nm in the visiblelight region was 70.5%, the transmittance at a wavelength of 800 nm was28.1%, the transmittance at a wavelength of 900 nm was 20.1%, thetransmittance at a wavelength of 1000 nm was 18.2%, and thetransmittance at a wavelength of 1500 nm was 69.4% in the near infraredregion. The transmission profile of the dried film of this dispersionliquid D is shown in FIG. 3.

Example 4

In the same manner as in example 1 except that 20 mass % of lanthanumhexaboride fine particles (average particle size of 1 to 2 μm) as nearinfrared absorbing fine particles, 10 mass % of dispersant “a” as adispersant, and 70.0 mass % of propylene glycol monomethyl ether acetate(abbreviated as PGM-Ac hereafter) were weighed, to thereby obtain ahexaboride fine particle dispersion liquid (abbreviated as a dispersionliquid E hereafter) of example 4.

Next, in the same manner as in example 1 except that the dispersionliquid E was used, a hexaboride fine particle dispersion liquid(abbreviated as a dispersion liquid F hereafter) of example 4 wasobtained. The concentration of lanthanum hexaboride fine particles inthe dispersion liquid F was 29.3 mass %.

An amount of residual PGM-Ac in the dispersion liquid F was measuredusing a dry moisture meter, and it was found to be 2.3 mass %. Thedispersed particle size of each hexaboride fine particle in thedispersion liquid F was measured using a particle size distributionmeter manufactured by Otsuka Electronics Co., and it was found to be84.7 nm, and a lattice constant was 0.41560 nm.

Next, in the same manner as in example 1, a dried film was obtained andthe optical properties were measured.

The obtained dried film had a visible light transmittance of 68.5%.Further, the transmittance at a wavelength of 550 nm in the visiblelight region was 70.6%, the transmittance at a wavelength of 800 nm was29.3%, the transmittance at a wavelength of 900 nm was 21.2%, thetransmittance at a wavelength of 1000 nm was 19.2%, and thetransmittance at a wavelength of 1500 nm was 70.8% in the near infraredregion. FIG. 4 shows a transmission profile of the dried film of thedispersion liquid F.

Comparative Example 1

20 mass % of lanthanum hexaboride fine particles (average particle sizeof 1 to 2 μm) as near infrared absorbing fine particles, 10 mass % ofdispersant “a” as a dispersant, 70 mass % of ethylene glycol having aboiling point of 197° C. as a solvent (abbreviated as E.G. hereafter)were weighed.

In the same manner as in example 1 except that these hexaboride fineparticles, dispersant and solvent were charged in a paint shakercontaining 0.3 mmφ ZrO₂ beads and pulverized and dispersed for 30 hoursto obtain a dispersion liquid of hexaboride fine particles ofcomparative example 1 (abbreviated as a dispersion liquid G hereafter),a hexaboride fine particle dispersion liquid (abbreviated as adispersion liquid H hereafter) of comparative example 1 was obtained.The concentration of the lanthanum hexaboride fine particles in thedispersion liquid H was 19.0 mass %.

An amount of residual E.G. in the dispersion liquid H was measured usinga dry moisture meter, and it was found to be 36.7 mass %.

The dispersed particle size of each hexaboride fine particle in thedispersion liquid H was measured using a particle size distributionmeter manufactured by Otsuka Electronics Co., and it was found to be83.7 nm. Further, the lattice constant was 0.41560 nm.

Next, in the same manner as in example 1 except that the dispersionliquid H was used, a dried film of comparative example 1 was prepared.However, due to large content of E. G, a dried film could not beobtained and the optical properties could not be measured.

Evaluation of Examples 1 to 4

In examples 1 to 4, the content of the first solvent in the seconddispersion liquid in which the hexaboride fine particles were dispersedin the vegetable oil was less than 5 mass %.

Further, the dried films of examples 1 to 4 show high transmittance inthe visible light region and the transmittance is remarkably low in thenear infrared region.

As a result, it was confirmed that the printed pattern prepared usingthe near infrared absorbing fine particle dispersion liquid of thepresent invention can be distinguished by a near infrared raydiscriminating machine.

Example 5

An example of preparing an anti-counterfeit ink B for offset printing(abbreviated as an ink B hereafter) using the dispersion liquid Bprepared in example 1, and a printing example using the ink B will bedescribed. However, the range of the present invention is not limited tothe description of these examples.

(Preparation of Rosin-Modified Phenolic Resin)

1000 parts by weight of P-octylphenol, 850 parts by weight of 35%formalin, 60 parts by weight of 93% sodium hydroxide, and 1000 parts byweight of toluene, were charged in a four-necked flask equipped with astirrer, a condenser, and a thermometer. Then, a mixture was allowed toreact at 90° C. for 6 hours. Thereafter, a hydrochloric acid solution of125 parts by weight of 6N hydrochloric acid and 1000 parts by weight ofwater was added, and after being stirred and left to stand, an upperlayer part was taken out. Then, 2000 parts by weight of a toluenesolution of a resol type phenol resin having a 49% nonvolatile contentwas obtained, which was used as a resol liquid.

1000 parts by weight of gum rosin was charged in a four-necked flaskequipped with a stirrer, a cooler with a moisture separator, and athermometer, and dissolved at 200° C. while blowing a nitrogen gastherein. 1,800 parts by weight of the resol liquid obtained above wasadded thereto, and the mixture was allowed to react at 230° C. for 4hours while removing toluene. After the reaction, 110 parts by weight ofglycerin was added and reacted at 250° C. for 10 hours so that the acidvalue was adjusted to 20 mg KOH/g or less, to thereby obtain arosin-modified phenol resin having a weight average molecular weight of50000, an opaque temperature of 88° C. in AF Solvent No. 6 produced byNippon Petrochemical Co., Ltd.

(Preparation of Varnish)

40 parts by weight of the rosin-modified phenol resin, 35 parts byweight of soybean oil, 24 parts by weight of AF Solvent No. 6 (solventmanufactured by Nippon Petrochemical Co., Ltd.), 1.0 part by weight ofALCH (gelling agent manufactured by Kawaken Fine Chemicals Co., Ltd.)were heated and stirred at 190° C. for 1 hour, to thereby obtain avarnish.

(Preparation of Anti-Counterfeit Ink for Offset Printing)

In a formulation shown in table 2, the dispersion liquid B prepared inexample 1, a varnish, a petroleum solvent (AF-6 Solvent manufactured byNippon Oil Corporation), soybean oil, tung oil, compound (manufacturedby GODO Ink: UG compound), a metal drier (937 dryer manufactured by DICGraphics Co., Ltd.), and a drying inhibitor (INKEEPER manufactured byTokyo Ink Co., Ltd.) were mixed, to thereby obtain an ink B. Theconcentration of lanthanum hexaboride in the ink B was 0.38 mass %. Theobtained offset printing ink did not cause agglomeration or the like andwas stable.

(Preparation of the Printed Matter)

White fine high-quality paper was prepared as a base material to beprinted and offset printing was performed using the ink B, to therebyobtain a printed matter B. An average value of the diffuse reflectanceof the obtained printed matter B in the wavelength range of 800 nm to1300 nm was 60.0%.

In contrast, the average value of the diffuse reflectance of the blankprinted matter of comparative example 2 described later in a wavelengthrange of 800 nm to 1300 nm was 77.7%.

Accordingly, a value obtained by dividing the average value of thediffuse reflectance of the printed matter B of example 5 in thewavelength range of 800 nm to 1300 nm, by the average value of thediffuse reflectance of the blank printed matter of comparative example 2in the wavelength range of 800 nm to 1300 nm described later was 0 77.

Example 6

In the same manner as in example 5 except that the dispersion liquid B,the varnish, the petroleum solvent, the soybean oil, the tung oil, thecompound, the metal drier, and the drying inhibitor prepared in example1 were mixed in the mixture shown in table 2, an anti-counterfeit ink C(abbreviated as an ink C hereafter) for offset printing was obtained.The concentration of lanthanum hexaboride in the ink C was 0.73 mass %.White fine high-quality paper was prepared as the base material to beprinted and offset printing was performed using the ink C, to therebyobtain a printed matter C. The average value of the diffuse reflectanceof the obtained printed matter C in the wavelength range of 800 nm to1300 nm was 46.3%.

Accordingly, the value obtained by dividing the average value of thediffuse reflectance of the printed matter C in the wavelength range of800 nm to 1300 nm, by the average value of the diffuse reflectance ofthe blank printed matter of the comparative example 2 in the wavelengthrange of 800 nm to 1300 nm was 0.60.

Example 7

In the same manner as in example 5 except that the dispersion liquid B,the varnish, the petroleum solvent, the soybean oil, the tung oil, thecompound, the metal drier, and the drying inhibitor prepared in example1 were mixed in the formulation shown in table 2, an anti-counterfeitink D (abbreviated as an ink D hereafter) for offset printing wasobtained. The concentration of lanthanum hexaboride in the ink D was1.86 mass %. White fine high-quality paper was prepared as the basematerial to be printed, and offset printing was performed using the inkD, to thereby obtain a printed matter D. The average value of thediffuse reflectance of the obtained printed matter D in the wavelengthrange of 800 nm to 1300 nm was 21.6%.

Accordingly, the value obtained by dividing the average value of thediffuse reflectance of the printed matter D in the wavelength range of800 nm to 1300 nm, by the average value of the diffuse reflectance ofthe blank printed matter of comparative example 2 in the wavelengthrange of 800 nm to 1300 was 0.28.

Comparative Example 2

In the same manner as in example 5 except that the varnish and thepetroleum solvent, soybean oil, tung oil, compound, metal drier, anddrying inhibitor were mixed in the formulation shown in table 2, ananti-counterfeit ink E (abbreviated as an ink E hereafter) for offsetprinting was obtained. White fine high-quality paper was prepared as thebase material to be printed and offset printing was performed using theink E, to thereby obtain a printed matter E as a blank printed matter.The average value of the diffuse reflectance of the obtained printedmatter E as a blank printed matter in the wavelength range of 800 nm to1300 nm was 77.7%.

Comparative Example 3

In the same manner as in example 1 except that antimony-doped tin oxide(ATO) fine particles (average particle size: 1 to 10 μm) was used as thenear infrared absorbing fine particles, a near infrared absorbing fineparticle dispersion liquid (abbreviated as a dispersion liquid Ihereafter) of comparative example 3 was obtained.

Next, in the same manner as in example 1 except that the dispersionliquid I was used, an antimony-doped tin oxide fine particle dispersionliquid (abbreviated as a dispersion liquid J hereafter) of comparativeexample 3 was obtained. The concentration of the antimony-doped tinoxide fine particles in the dispersion liquid J was 29.3 mass %.

Here, an amount of residual MIBK in the dispersion liquid J was measuredusing a dry moisture meter, and it was found to be 2.3 mass %. Thedispersed particle size of each antimony-doped tin oxide fine particlein the dispersion liquid J was measured, and it was found to be 75.6 nm.

In the same manner as in example 5 except that the dispersion liquid J,the varnish, the petroleum solvent, the soybean oil, the tung oil, thecompound, the metal drier, and the drying inhibitor prepared in theformulation shown in table 2 were mixed, an anti-counterfeit ink F foroffset printing (abbreviated as an ink F hereafter) was obtained. Whitefine high-quality paper was prepared as the base material to be printedand offset printing was performed using the ink F, to thereby obtain aprinted matter F. The average value of the reflectance of the obtainedprinted matter F in the wavelength range of 800 nm to 1300 nm was 70.3%.

Accordingly, the value obtained by dividing the average value of thediffuse reflectance of the printed matter F in the wavelength range of800 nm to 1300 nm, by the average value of the diffuse reflectance ofthe blank of comparative example 2 in the wavelength range of 800 nm to1300 nm was 0.90.

Evaluation of Examples 5 to 7 and Comparative Examples 2 and 3

In examples 5 to 7, printed matters B to D containing hexaboride fineparticles in the printed pattern, show low diffuse reflectance in thewavelength range of 800 to 1300 nm. The value obtained by dividing theaverage value of the diffuse reflectance in the wavelength range of 800nm to 1300 nm, by the average value of the diffuse reflectance of theblank in the wavelength range of 800 nm to 1300 nm is as small as 0.28to 0.77. As a result, it was confirmed that the authenticity of theprinted matter containing hexaboride particles was easily judged.

In contrast, the printed matter E containing hexaboride fine particlesin the printed pattern of comparative example 2 and the printed matter Fcontaining antimony-doped tin oxide fine particles in the printedpattern of comparative example 3, show high diffuse reflectance in thewavelength range of 800 nm to 1300 nm. The value obtained by dividingthe average value of the diffuse reflectance in the wavelength range of800 nm to 1300 nm, by the average value of the diffuse reflectance ofthe blank in the wavelength range of 800 nm to 1300 nm is as large as0.90 to 1.00, and judgment of authenticity is considered to be difficultby the reflectance in the wavelength range of 800 nm to 1300.

Further, in the case of obtaining the printed matter whose authenticityis easily judged by the printing ink containing antimony-doped tin oxidefine particles of comparative example 3, the thickness of the ink on thesurface of the printed matter is required to be increased so that it canbe visually recognized, and it is considered not practical to use such aprinted matter for preventing counterfeiting.

[Table 1] [Table 2]

1. An anti-counterfeit ink composition for offset printing, comprising:a near infrared absorbing fine particle dispersion liquid, a resinvarnish component, a vegetable oil component, a petroleum solventcomponent, and an additive agent, wherein the near infrared absorbingfine particle dispersion liquid comprises a solvent of vegetable oils orvegetable oil-derived compounds; near infrared absorbing fine particlesof hexaboride fine particles expressed by a general formula XBa (whereinelement X is at least one or more kinds selected from a group consistingof La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, andCa, satisfying 4.0≤a≤6.2); a solvent of one or more kinds selected fromthe group consisting of alcohols, ethers, esters, ketones, and glycolethers and having a boiling point of 180° C. or less; and a dispersantwhich is soluble in the solvent of one or more kinds selected from thevegetable oils or vegetable oil-derived compounds and has a fatty acidin its structure, wherein content of the solvent of one or more kindsselected from the group consisting of alcohols, ethers, esters, ketones,and glycol ethers is 0.0195 mass % or more and 1.0 mass % or less in theanti-counterfeit ink composition for offset printing.
 2. Theanti-counterfeit ink composition for offset printing according to claim1, wherein the dispersant is contained at 30 parts by weight or more and200 parts by weight or less based on 100 parts by weight of thehexaboride fine particles.
 3. The anti-counterfeit ink composition foroffset printing according to claim 2, wherein an anchor portion of thedispersant has one or more kinds selected from the group consisting of asecondary amino group, a tertiary amino group, and a quaternary ammoniumgroup.
 4. The anti-counterfeit ink composition for offset printingaccording to claim 2, wherein the dispersant has an acid value of 1 mgKOH/g or more.
 5. The anti-counterfeit ink composition for offsetprinting according to claim 1, wherein a dispersed particle size of thenear infrared absorbing fine particles is 1 nm or more and 200 nm orless.
 6. The anti-counterfeit ink composition for offset printingaccording to claim 1, wherein a lattice constant of the near infraredabsorbing fine particles is 0.4100 nm or more and 0.4160 nm or less. 7.The anti-counterfeit ink composition for offset printing according toclaim 1, wherein a surface of the near infrared absorbing fine particlesis coated with a compound of one or more kinds selected from the groupconsisting of Si, Ti, A1, and Zr.
 8. The anti-counterfeit inkcomposition for offset printing according to claim 1, wherein thevegetable oil is drying oil or semidrying oil.
 9. The anti-counterfeitink composition for offset printing according to claim 1, furthercomprising a pigment.
 10. The anti-counterfeit ink composition foroffset printing according to claim 9, wherein the pigment is aninorganic pigment, and is one or more kinds selected from the groupconsisting of carbon black, white pigment, an extender pigment, a redpigment, a yellow pigment, a green pigment, a blue pigment, a purplepigment, a fluorescent pigment, a temperature indicating pigment, apearl pigment, and a metal powder pigment.
 11. The anti-counterfeit inkcomposition for offset printing according to claim 9, wherein thepigment is an organic pigment and is one or more kinds selected from anazo lake pigment, an insoluble azo pigment, a condensed azo pigment, aphthalocyanine pigment, and a condensed polycyclic pigment.
 12. Theanti-counterfeit ink composition for offset printing according to claim1, further comprising one or more kinds selected from the groupconsisting of a plasticizer, an antioxidant, a thickener, and a wax. 13.An anti-counterfeit printed matter, having a printed pattern on one sideor both sides of a base material, wherein the printed pattern is printedby using the anti-counterfeit ink composition for offset printing ofclaim 1 in an offset printing.
 14. The anti-counterfeit printed matteraccording to claim 13, wherein the printed pattern further contains apigment.
 15. The anti-counterfeit printed matter according to claim 14,wherein the pigment is an inorganic pigment and is one or more kindsselected from the group consisting of carbon black, white pigment, anextender pigment, a red pigment, a yellow pigment, a green pigment, ablue pigment, a purple pigment, a fluorescent pigment, a temperatureindicating pigment, a pearl pigment, and a metal powder pigment.
 16. Theanti-counterfeit printed matter according to claim 14, wherein thepigment is an organic pigment, and is one or more kinds selected fromthe group consisting of an azo lake pigment, an insoluble azo pigment, acondensed azo pigment, a phthalocyanine pigment, and a condensedpolycyclic pigment.
 17. The anti-counterfeit printed matter according toclaim 13, wherein a value obtained by dividing an average value of adiffuse reflectance of the anti-counterfeit printed matter in awavelength range of 800 nm to 1300 nm, by an average value of a diffusereflectance of a blank not containing the near infrared absorbing fineparticles in the wavelength range of 800 nm to 1300 nm, is 0.84 or less.18. The anti-counterfeit ink composition for offset printing accordingto claim 1, wherein the solvent having the boiling point of 180° C. orless is one or more kinds selected from the group consisting of ethers,esters, and glycol ethers.